CN112592505B - Hard coating film, window comprising same, and image display device - Google Patents

Hard coating film, window comprising same, and image display device Download PDF

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Publication number
CN112592505B
CN112592505B CN202011031622.2A CN202011031622A CN112592505B CN 112592505 B CN112592505 B CN 112592505B CN 202011031622 A CN202011031622 A CN 202011031622A CN 112592505 B CN112592505 B CN 112592505B
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hard coating
weight
fluorine
film
meth
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CN112592505A (en
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姜敏憼
林巨山
金承熙
金慧璘
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Dongwoo Fine Chem Co Ltd
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Dongwoo Fine Chem Co Ltd
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Abstract

The present invention provides a hard coating film including a substrate; and a hard coating layer provided on at least one surface of the substrate, wherein the surface resistivity of the hard coating layer is 10 8 ～10 12 Ω/≡, water contact angle is at least 100 °.

Description

Hard coating film, window comprising same, and image display device
Technical Field
The present invention relates to a hard coat film, and a window and an image display device including the same.
Background
A Flexible display (Flexible) has been proposed as a display capable of being bent or folded. If the display is designed into a foldable form, the display with different sizes can be used as a product, namely, can be used as a tablet computer (tablet) after being unfolded, and can be used as a smart phone after being folded. In addition, compared with a smart phone with smaller size, if the smart phone is a device with larger size such as a tablet personal computer or a TV, the smart phone can be carried with the user after being folded, and is more convenient.
In the case of a general display, a glass cover window (cover window) for protecting the display is provided at the outermost portion. However, in the case of glass, it cannot be used for foldable displays. In order to be able to replace glass, high-hardness hard coating films having high hardness and abrasion resistance are currently being used.
In addition, since an optical component such as a polarizer included in such a display is made of a plastic material, static electricity is generated during rubbing and peeling, and when a voltage is applied to liquid crystal in a state where static electricity is left, the alignment of liquid crystal molecules is lost or a panel is damaged, and various antistatic measures are performed to prevent these problems.
Recently, a hard coating film is required to have hard coating properties, and at the same time, stain resistance related to resistance and/or easy-to-clean property due to marks such as fingerprints and markers is required as its main performance.
Korean laid-open patent No. 2012-011683 relates to an ultraviolet curable antifouling and antistatic hard coating composition and an antifouling and antistatic plastic panel using the same. In the document, an ultraviolet-curable antifouling and antistatic hard coating composition is cured by ultraviolet irradiation to form a coating layer, the ultraviolet-curable resin content is 3 to 30 parts by weight, the fluorine-containing denatured multifunctional acrylate compound content is 0.01 to 3 parts by weight, the electroconductive polymer solution content is 5 to 30 parts by weight, the photopolymerization initiator content is 0.1 to 5 parts by weight, and the electroconductive polymer affinity polar organic solvent content is 30 to 90 parts by weight, relative to 100 parts by weight of the entire composition. The ultraviolet-curable antifouling and antistatic hard coating composition of the document has a hardness of 3H or more and a surface resistivity of 10 as a hard coating cured by ultraviolet irradiation 6 ～10 8 Omega/≡, water contact angle is more than or equal to 95 degrees, visible light transmittance is more than or equal to 92 degrees, and haze value is more than or equal to 0.5%.
Further, korean laid-open patent No. 2014-0095573 relates to a laminate in which a cured resin layer [ II ] having a contact angle with water of at least 100 ° is formed on at least one surface of a resin molded body [ I ] obtained by curing a photocurable composition (I), and uses thereof.
However, when friction experiments were carried out in the prior art, it was found that the abrasion resistance was lowered, the initial contact angle was not maintained well, or the antistatic property was not exhibited, and the laminate was not preferable in terms of the process.
Therefore, development of a hard coating film which is applicable to flexible displays, has good antistatic properties, and has both abrasion resistance and stain resistance has been desired.
Prior art literature
Patent literature
Korean laid-open patent No. 2012-011683 (2012.10.19)
Korean laid-open patent No. 2014-0095573 (2014.08.01)
Disclosure of Invention
Technical problem
The present invention relates to a hard coating film having excellent antistatic properties and simultaneously abrasion resistance and stain resistance.
The present invention also provides a high-hardness hard coating film.
In addition, the present invention provides a window comprising the hard coating film.
In addition, the invention provides an image display device comprising the window.
Technical proposal
The present invention provides a hard coating film comprising a substrate; and a hard coating layer provided on at least one surface of the substrate, wherein the surface resistivity of the hard coating layer is 10 8 ～10 12 Ω/≡, water contact angle is at least 100 °.
In addition, the present invention provides a window comprising the hard coat film.
In addition, the present invention provides an image display device including: the window and the display panel; further comprises: and a touch sensor and a polaroid are arranged between the window and the display panel.
Advantageous effects
The hard coating film according to the present invention has advantages of excellent hardness and antistatic properties, and also has abrasion resistance and stain resistance, and is applicable to windows of flexible display devices in addition to image display devices because of excellent flex resistance.
Drawings
Fig. 1 is a schematic diagram showing a structure of an image display device according to an embodiment of the invention.
Detailed Description
The present invention will be described in more detail below.
In the present invention, when it is referred to that a certain component is "on" another component, this includes both the case where the certain component is directly engaged with the other component and the case where the other component is interposed between the two components.
In the present invention, when a certain portion "includes" a certain constituent element, it is not meant to exclude other constituent elements, but it may also mean to include other constituent elements unless otherwise specified.
In one aspect of the present invention, there is provided a hard coat film comprising a substrate; and a hard coating layer provided on at least one surface of the substrate, wherein the surface resistivity of the hard coating layer is 10 8 ～10 12 Ω/≡, water contact angle is at least 100 °.
The hard coating film according to the present invention has the advantages of good hardness, antistatic properties, abrasion resistance and high stain resistance. In particular, the hard coating film according to the present invention can also maintain excellent abrasion resistance.
The surface resistivity of the hard coating according to the invention was 10 8 ～10 12 Ω/≡. Since the hard coating according to the present invention has the surface resistivity within the range, it has excellent mechanical strength and also has excellent antistatic properties.
According to an embodiment of the present invention, preferably, the surface resistivity of the hard coating layer is 10 9 ～10 12 Ω/≡. The antistatic property may be more excellent when the surface resistivity of the hard coating layer satisfies the range.
The water contact angle of the hard coating according to the invention is at least 100. According to the present invention, the water contact angle refers to an angle formed by water drops on a hard coating surface when the water drops fall on the hard coating surface, and foreign matters are more difficult to adhere to the coating surface as the water contact angle is larger, so that the antifouling property such as fingerprint prevention is more excellent. In addition, since the surface alignment of the fluorine material of the fluorine-based solvent is increased, the properties of the antifouling property other than the initial antifouling property, that is, the abrasion resistance, can be maintained more excellent.
In summary, the hard coating according to the present invention has advantages of excellent abrasion resistance and stain resistance due to the water contact angle of 100 ° or more.
According to another embodiment of the invention, the hard coating has a contact angle of at least 100 ° after 3000 rubs with a wiper and a 1kg weight.
Preferably, the hard coating has a contact angle of at least 102 °, more preferably at least 105 °, after 3000 rubs with a wiper and a 1kg bob.
In summary, the hard coating according to the present invention is excellent in abrasion resistance and in retention of stain resistance.
The hard coating film according to the present invention comprises a substrate, in particular a transparent substrate.
The substrate is not particularly limited as long as it is a substrate commonly used in the art, and specifically, a film excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like can be used.
More specifically, the film comprises: polyester resins such as polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate and polybutylene terephthalate; cellulose resins such as diacetyl cellulose and triacetyl cellulose; a polycarbonate resin; acrylic resins such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; styrene resins such as polystyrene and acrylonitrile-styrene copolymer; polyolefin resins such as polyolefin having a polyethylene, polypropylene, cycloolefin or norbornene structure, and ethylene-propylene copolymer; vinyl chloride resin; amide resins such as nylon and aromatic polyamide; imide-based resins; sulfone resins; polyether sulfone resins; polyether-ether-ketone resin; polyphenylene sulfide resin; vinyl alcohol resin; vinylidene chloride resin; a vinyl butyral resin; an allyl ester resin; a polyoxymethylene resin; at least one kind of thermoplastic resin such as epoxy resin. In addition, a film comprising the thermoplastic resin mixture may also be used. Further, a film containing a thermosetting resin such as (meth) acrylic, urethane, acrylic urethane, epoxy, or silicon and/or an ultraviolet curable resin may be used. According to an embodiment of the present invention, a polyimide resin which is more easily applicable to a flexible image display device excellent in repeated bending durability can be used, and a polyimide resin film or a polyester resin film can be used together.
The thickness of the substrate is 20 to 100. Mu.m, preferably 30 to 80. Mu.m. When the thickness of the base material is within the above range, the strength of the hard coating film containing the base material is improved, and thus the workability is improved, and the occurrence of a phenomenon of lowering of transparency can be prevented, while the weight of the film can be reduced.
According to another embodiment of the present invention, the hard coat layer includes: a cured product of a hard coating composition comprising a fluorine-containing UV curable functional group compound, a fluorine-containing solvent, and an antistatic agent. The hard coating according to the present invention is formed using a fluorine-containing UV curable functional group-containing compound, a fluorine-containing solvent, and an antistatic agent, and therefore, not only is excellent in antistatic properties, abrasion resistance, and stain resistance, but also these properties can be well maintained.
The fluorine-containing UV curable functional group-containing compound is a structure used for the purpose of having stain resistance, abrasion resistance, or chemical resistance, and therefore, it is necessary to contain a fluorine component and also have a UV curable functional group so as to be capable of chemically bonding with other structures, and the kind thereof is not limited as long as it satisfies the present invention.
According to another embodiment of the present invention, the fluorine-containing UV curable functional group-containing compound includes: at least one selected from the group consisting of perfluoroalkyl group-containing (meth) acrylates, perfluoropolyether group-containing (meth) acrylates, perfluorocyclic aliphatic group-containing (meth) acrylates, and perfluoroaromatic group-containing (meth) acrylates. In this case, chemical bonding with the hard coating layer is formed while excellent antifouling performance is exhibited, and the antifouling performance is maintained for a long time even after repeated use, so that the durability thereof is very excellent.
As the fluorine-containing UV curable compound, commercially available ones such as KY-1203, FS-7025, FS-7026, FS-7031, and FS-7032 are available, but not limited thereto.
According to another embodiment of the present invention, the fluorine-containing UV curable functional group-containing compound may be contained in an amount of 0.01 to 30 wt%, preferably 0.01 to 20 wt%, based on 100 wt% of the total solids in the hard coating composition; more preferably, the content thereof is 0.01 to 10% by weight.
When the content of the fluorine-containing UV curable functional group-containing compound is within the above range, the effect of excellent abrasion resistance and antifouling property can be imparted. When the fluorine-containing UV curable functional group-containing compound does not fall within the above range, it is difficult to sufficiently support the abrasion resistance and the stain resistance, and when it exceeds the above range, the film hardness and the abrasion resistance are rather lowered, and therefore, it is preferable to fall within the above range.
The fluorine-based solvent is used for improving the solubility with fluorine-based compounds and reducing the friction coefficient to improve the slidability.
The fluorine-based solvent content is 0.1 to 50 wt%, preferably 0.1 to 40 wt%, more preferably 1 to 20 wt%, relative to 100 wt% of the whole hard coating composition.
When the fluorine-based solvent is contained in the above range, the surface of the fluorine-based UV curable functional group-containing compound can be kept in a sufficient amount, and the coatability and the film coating state of the film are excellent.
According to another embodiment of the present invention, the fluorine-based solvent includes at least one selected from the group consisting of perfluorohexyl ethanol, perfluoroether, perfluorohexane.
Specifically, the fluorine-based solvent is at least one of the following chemical formulas 1 to 8.
[ chemical formula 1]
Figure BDA0002703934900000061
[ chemical formula 2]
Figure BDA0002703934900000062
[ chemical formula 3]
Figure BDA0002703934900000063
[ chemical formula 4]
Figure BDA0002703934900000071
[ chemical formula 5]
Figure BDA0002703934900000072
[ chemical formula 6]
Figure BDA0002703934900000073
[ chemical formula 7]
Figure BDA0002703934900000081
[ chemical formula 8]
Figure BDA0002703934900000082
Commercial products of the fluorine-based solvent include, but are not limited to, 3M company HFE-7100, HFE-7300, HFE-7500, FC-3283, FC-40, FC-770, NICCA company C6FOH-BF, and the like.
The antistatic agent may be any one as used in the art. Specifically, at least one of ionic liquid, conductive polymer, lithium salt, quaternary ammonium salt, metal oxide particles, and the like is included, but not limited thereto.
More specifically, the ionic liquid may be imidazolines, ammonium, pyrazines, thiazoles, but is not limited thereto, and the conductive polymer may be polyaniline, or a poishiophene polymer, but is not limited thereto. In addition, the metal oxide particles may include SnO 2 ,TiO 2 ,Fe 2 O 3 At least one of the following.
The antistatic agent content is 0.01 to 50 wt%, preferably 0.1 to 30 wt%, based on 100 wt% of the whole hard coating composition, and in this case, it is possible to suppress the decrease of mechanical strength and to exhibit excellent antistatic performance.
According to another embodiment of the present invention, the hard coating composition further includes at least one selected from the group consisting of a light transmissive resin, a photoinitiator, an additional solvent, and an additive.
In the present invention, the light-transmitting resin refers to a light-curable resin, and the light-curable resin may include a light-curable (meth) acrylate oligomer and/or monomer, but is not limited thereto.
The photo-curable (meth) acrylate oligomer includes at least one of epoxy (meth) acrylate, urethane (meth) acrylate, and ester (meth) acrylate, and preferably, urethane (meth) acrylate, but is not limited thereto.
The polyurethane (meth) acrylate can produce a polyfunctional (meth) acrylate having a hydroxyl group in the molecule and a compound having an isocyanate group in the presence of a catalyst.
Specific examples of the (meth) acrylate having a hydroxyl group in the molecule include: at least one selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxyisopropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone ring-opened hydroxyacrylate, pentaerythritol tri/tetra (meth) acrylate mixture, and dipentaerythritol penta/hexa (meth) acrylate mixture.
In addition, specific examples of the compound having the isocyanate group include: at least one selected from the group consisting of 1, 4-diisocyanatobutane, 1, 6-diisocyanatohexane, 1, 8-diisocyanatooctane, 1, 12-diisocyanatodridecane, 1, 5-methylenebis (2, 6-dimethylphenyl isocyanate), trimethyl-1, 6-diisocyanatohexane, 1, 3-bis (isocyanatomethyl) cyclohexane, trans-1, 4-cyclohexyldiisocyanate, 4' -methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, toluene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, xylene-1, 4-diisocyanate, tetramethyl-xylene-1, 3-diisocyanate, 1-chloromethyl-2, 4-diisocyanate, 4' -methylenebis (2, 6-dimethylphenyl isocyanate), 4' -oxidized bis (phenyl isocyanate), 3-functional isocyanate derived from hexamethylene diisocyanate and trimethylalkyl propanol adducts of toluene diisocyanate.
The monomers may be used in common applications, for example: the photohardening functional group may include an unsaturated group having a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group, or the like in a molecule, and among these, (meth) acryloyl groups are preferable.
Specific examples of the monomer having the (meth) acryl group include: selected from the group consisting of neopentyl glycol acrylate, 1, 6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, 1,2, 4-cyclohexane tetra (meth) acrylate, pentapolyglycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tri (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, at least one kind selected from the group consisting of phenoxyethyl (meth) acrylate and isobornyl (meth) acrylate.
The photo-curable (meth) acrylate oligomer and monomer shown as the light-transmitting resin may be used singly or in combination of two or more.
The light-transmitting resin is not particularly limited, but the content of the light-transmitting resin is 1 to 80% by weight, preferably 10 to 80% by weight, more preferably 30 to 70% by weight, and most preferably 32 to 60% by weight, relative to 100% by weight of the entire hard coating composition. When the light-transmitting resin is contained in the range, an effect of sufficiently improving the hardness can be obtained, and there is an advantage that the curling phenomenon can be suppressed.
The photoinitiator is included to induce photo-hardening of the hard coating composition, for example, a photo-radical initiator that can form radicals by light irradiation may be included.
The photoinitiator may include, for example, a Type 1 initiator that can decompose a molecule by a chemical structure or a molecular binding energy difference to generate a radical, a Type 2 initiator by coexisting with a tertiary amine to induce hydrogen abstraction, and the like.
For example, the Type 1 initiator includes acetaminophen such as 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, 4-t-butyltrichloroacetophenone, dioxyacetophenone, 2-hydroxy-2-methyl-l-phenylpropane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-l-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, and the like; benzoin such as benzoin methyl ether, ethyl benzoin ether and benzyl dimethyl ketal; at least one of phosphine oxides and titanocene compounds. For example, the Type 2 initiator may include at least one of benzophenone compounds such as benzophenone, benzoyl benzoic acid, methyl ethyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, 4-benzene-4 '-methyl diphenyl sulfide, 3' -methyl-4-methoxy benzophenone, thioxanthone compounds such as 2-chlorothioxanthone, 2-methylthioxanthone, 2, 4-dimethylthioxanthone, isopropyl thioxanthone, etc.
The photoinitiators may be used individually or in combination of at least two, that is, type 1 and Type 2 may be used in combination.
The photoinitiator is used in an amount of 0.1 to 10% by weight, preferably 1 to 8% by weight, more preferably 1 to 6% by weight, relative to 100% by weight of the entire hard coating composition. When the content of the photoinitiator is within the above range, the hardening speed can be increased, the occurrence of unhardened phenomenon can be suppressed, excellent mechanical properties can be maintained, and the occurrence of cracks in the coating film due to excessive hardening can be suppressed.
The hard coating composition further includes an additional solvent other than the fluorine-based solvent. The additional solvent may allow the composition to be uniformly mixed and reduce the viscosity of the composition to facilitate coating.
Preferably, the additional solvent may use alcohols (methanol, ethanol, isopropanol, butanol, methyl cellosolve, ethyl cellosolve, etc.), ketones (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, cyclohexanone, etc.), acetic acids (ethyl acetate, propyl acetate, n-butyl acetate, t-butyl acetate, methoxyethyl acetate, ethoxyethyl acetate, propylene glycol monomethyl ether acetate, methoxyethanol acetate, methoxybutyl acetate, methoxypentyl acetate, etc.), hexane (hexane, heptane, octane, etc.), benzene (benzene, toluene, xylene, etc.), ethers (diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol methyl ether, etc.). The solvents in the examples may be used alone or in combination of at least 2 or more.
The content of the additional solvent is 10 to 95% by weight, preferably 10 to 80% by weight, more preferably 20 to 60% by weight, relative to 100% by weight of the entire hard coating composition. When the content of the additional solvent is within the range, the viscosity is moderate, the workability is excellent, the expansibility of the base film can be sufficiently embodied, the time can be shortened in the drying process, and excellent economy can be maintained. Therefore, the amount used is preferably within the range.
The additives are, for example, ultraviolet stabilizers, heat stabilizers, polymer compounds commonly used in the art, photostimulants, antioxidants, thermal inhibitors, surfactants, lubricants, antifouling agents, etc.
Since the surface of the cured coating film is decomposed and discolored by being continuously exposed to ultraviolet rays and is easily broken for a long time, the ultraviolet stabilizer is an additive added for blocking or absorbing the ultraviolet rays for the purpose of protecting the adhesive.
The ultraviolet stabilizer comprises: at least one of an absorber, a matting agent (matting agent), a hindered amine light stabilizer (HALS, hindered Amine Light Stabilizer) classified according to mechanism of action; in addition, the method comprises: at least one of phenyl salicylate (Phenyl Salicylates, absorber), benzophenone (benzoquinone, absorber), benzotriazole (absorber), nickel derivative (matting agent), radical scavenger (Radical Scavenger) classified according to chemical structure; in addition, the method comprises the following steps: ultraviolet stabilizers commonly used in the art.
The heat stabilizer as a product useful for commercial purposes includes: the heat stabilizer 1 is at least one of polyphenols, and the heat stabilizer 2 is at least one of phosphites and lactones, but is not limited thereto.
The ultraviolet stabilizer and the heat stabilizer may be used by appropriately adjusting the content thereof within the standard that does not affect the ultraviolet curability.
The additives can be further included within a range that does not hinder the effect of the present invention, and a person skilled in the art can appropriately select when selecting a specific kind or controlling the content.
The hard coating film according to the present invention may be formed by coating the hard coating composition on one or both surfaces of the substrate and then hardening it.
When a hard coat film is formed using the hard coat composition, a 1-pass coating method may be employed. In summary, even in the case of using a single-layer hard coating, excellent antistatic properties, abrasion resistance and antifouling properties can be simultaneously imparted thereto. The properties such as antistatic property, abrasion resistance and antifouling property can be maintained even when the hard coating film is rubbed. At the same time, high hardness can be imparted.
In summary, the hard coating layer comprising the hardened substance of the hard coating composition according to the present invention, the hard coating film comprising the hard coating layer exhibits excellent antistatic property, high hardness, and at the same time has the advantage of excellent abrasion resistance and stain resistance.
The hard coat layer may be applied by a suitable means such as a die coater, air knife, reverse roll, spray gun, blade, casting, gravure coating, micro gravure coating, spin coating, and the like.
The thickness of the coating layer is 1 μm to 200 μm, specifically, 3 μm to 100 μm, more specifically, 3 μm to 30 μm, but is not limited thereto. However, when the thickness of the coating layer satisfies the above range, a hard coating film having the advantages of excellent hardness, flexibility, thickness reduction, and maintenance of antistatic properties, abrasion resistance, stain resistance, and the like can be produced. The thickness of the coating refers to the thickness after drying.
After the hard coating composition is coated, it is dried at a temperature of 30 to 150 ℃ for 10 seconds to 1 hour. Specifically, it is dried by evaporating its volatiles over a period of 30 seconds to 10 minutes. The hard coating composition is then hardened by irradiation with UV light. The irradiation amount of the UV light is about 200-2000 mJ/cm 2 Specifically, the irradiation amount thereof is 200 to 1500mJ/cm 2 。
The hardcoat film can be used in flexible displays. Specifically, the glass cover sheet can be used as a cover glass for replacing a display such as LCD, OLED, LED, FED or various mobile communication terminal devices, touch panels of smart phones or tablet computers, electronic paper and the like which adopt the display, or used for a functional layer.
Another aspect of the invention relates to a window comprising the hardcoat film.
The window serves to protect the constituent elements included in the image display device from external impact or ambient temperature and humidity changes. A light shielding pattern may be formed on a peripheral portion of one surface of the window. For example: the light shielding pattern may also include a color printed pattern, and may have a single-layer or multi-layer structure. An outer frame portion or a non-display area of the image display apparatus may be defined by the light shielding pattern.
In still another aspect, the present invention relates to an image display apparatus, comprising: the window 100 and the display panel 200. In addition, a touch sensor 300 and a polarizer 400 are further included between the window 100 and the display panel 200.
The image display device includes, but is not limited to, a liquid crystal display, an OLED, a flexible display, etc., and all image display devices known in the art that can be employed can be cited.
The display panel 200 includes, but is not limited to: the pixel electrode, the pixel definition film, the display layer, the counter electrode and the packaging layer are arranged on the panel substrate. The method further comprises the following steps according to the need: construction used in the art.
As an example, a pixel circuit including a Thin Film Transistor (TFT) may be formed on the panel substrate, and an insulating film covering the pixel circuit may be formed. In this case, for example: the pixel electrode may be electrically connected to a drain electrode of the TFT on the insulating film. The pixel defining film is formed on the insulating film to expose the pixel electrode to the outside, so that a pixel region can be defined. A display layer may be formed on the pixel electrode, for example: the display layer includes a liquid crystal layer or an organic light emitting layer. Counter electrodes may be provided on the pixel definition film and the display layer, for example: the counter electrode may be used as a common electrode or a cathode of the image display device. An encapsulation layer protecting the display panel may be laminated on the counter electrode.
The touch sensor 300 is used as an input means, for example: the touch sensor 300 may be provided in various forms such as a resistive film type, a surface elastic wave type, an infrared type, an electron induction type, and a capacitance type, and the capacitance type is preferably used although the present invention is not particularly limited to a certain form.
The electrostatic capacity type touch sensor is divided into an active area and an inactive area positioned at the periphery of the active area. The active region is a region corresponding to a region (display portion) displayed on the screen of the display panel, and the inactive region is a region corresponding to a region (non-display portion) not displayed on the screen of the display device. A touch sensor, comprising: a substrate having toughness; a sensing pattern (pattern) formed on an active region of the substrate; and each sensing line formed in the inactive region of the substrate and connected to an external driving circuit through the sensing pattern and the pad portion. The substrate having toughness may be the same material as the transparent base material of the window. In addition, toughness (toughness) is defined as a lower area of a curve from Stress (MPa) -deformation (%) obtained by a tensile test of a polymer material to a failure point, and the touch sensor substrate preferably has toughness of at least 2,000MPa%, and from the aspect of suppressing cracks of the touch sensor, the effect is more desirable, and more preferably, toughness is 2,000MPa% to 30,000MPa%.
The sensing pattern comprises a 1 st pattern formed along a 1 st direction and a 2 nd pattern formed along a 2 nd direction, and the 1 st pattern and the 2 nd pattern are configured along different directions. In order to sense the touch position formed on the same layer, the 1 st and 2 nd patterns must be electrically connected to each other. Although the 1 st pattern is formed in a form of being connected to each other by each unit pattern Fitting (patterning), each unit pattern of the 2 nd pattern is in an "island-like" form, and is structurally separated from each other. Therefore, in order to electrically connect the 2 nd pattern, a bridge electrode needs to be additionally provided. The sensing pattern may employ a well-known transparent electrode material, for example: including Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), zinc oxide (ZnO), indium Zinc Tin Oxide (IZTO), cadmium Tin Oxide (CTO), PEDOT (poly (3, 4-ethylenedioxythiophene)), carbon Nanotubes (CNT), graphene, wires, and the like, which may be used singly or in combination of at least two. Preferably, ITO may be used. The metal used for the wire is not particularly limited, for example: silver, gold, aluminum, copper, iron, nickel, titanium, selenium (selenium), chromium, etc., which may be used singly or in combination of at least two.
The bridge electrode may be formed on the upper portion of the insulating layer by interposing the insulating layer on the upper portion of the sensing pattern, and the bridge electrode may be disposed on the substrate, and the insulating layer and the sensing pattern may be formed thereon. The bridge electrode may be made of the same material as the sensing pattern, or may be made of a metal such as molybdenum, silver, aluminum, copper, palladium, gold, platinum, zinc, tin, titanium, or an alloy of at least two of them. Since the 1 st pattern and the 2 nd pattern must be electrically connected, an insulating layer is formed between the sensing pattern and the bridge electrode. The insulating layer may be formed only between the 1 st pattern of the metal fitting and the bridge electrode, or may be formed in a layered structure covering the sensing pattern. In the latter case, the bridge electrode may be connected to the 2 nd pattern through a contact hole provided on the insulating layer. As a method of appropriately compensating for the difference in transmittance between the pattern region where the sensing pattern is formed and the non-pattern region where the pattern is not formed, in particular, as a method of appropriately compensating for the difference in transmittance induced by the difference in refractive index of the portion, an optical adjustment layer may be further provided between the substrate and the electrode, and the optical adjustment layer may be formed by applying a photo-setting composition containing a photo-setting organic binder on the substrate. The photohardening composition further comprises inorganic particles, which may increase the refractive index of the optical adjustment layer.
The photocurable organic adhesive comprises: for example, copolymers of various monomers such as acrylic monomers, styrene monomers, and carboxylic acid monomers. For example: the photocurable organic binder may be a copolymer having repeating units such as an epoxy group-containing repeating unit, an acrylate repeating unit, and a carboxylic acid repeating unit, which are different from each other.
The inorganic particles include, for example, zirconia particles, titania particles, alumina particles, and the like. The photo-hardening composition further comprises various additives such as a photopolymerization initiator, a polymerizable monomer, a hardening aid, and the like.
The polarizer 400 may be either a structure using a polarizer alone or a structure of preparing a transparent substrate attached to at least one surface thereof on the basis of a polarizer. The polarizing states of light emitted through the polarizer are classified into a linear polarizer, a circular polarizer, and the like. Although there is no particular limitation in the present invention, a circular polarizer for improving the recognition (recognition degree) by absorbing reflected light will be specifically described below.
The circular polarizer is a functional layer having a function of allowing only right or left circularly polarized light components to pass through by laminating a lambda/4 retardation plate on a linear polarizer, for example: the external light is converted into right circularly polarized light, and after being reflected on the organic EL panel, the external light constituting left circularly polarized light is blocked, and only the light-emitting component of the organic EL is transmitted, so that the influence of the reflected light can be suppressed, and the image can be recognized more easily. In order to realize the circularly polarized light function, the absorption axis of the linear polarizer should theoretically be 45 ° to the ground axis of the λ/4 retardation plate, but may be 45±10° from the practical point of view. The linear polarizer and the lambda/4 phase difference plate do not necessarily have to be laminated adjacently as long as the relationship of the absorption axis and the above-ground axis can satisfy the range. Although it is desirable to use the complete circularly polarized light effect in all wavelength ranges, this is not necessarily so from a practical point of view. Therefore, the circular polarizer of the present invention further includes an elliptical polarizer. In order to be closer to the recognition side of the linear polarizer, the outgoing light is converted into circularly polarized light by laminating a lambda/4 retardation film. Therefore, the recognition degree of the linear polaroid sandwiched between the linear polaroids can be improved, and the effect of the mode is ideal.
Although the linear polarizer passes only light vibrating in the transmission axis direction, it is actually a functional layer having a polarization blocking function of vibrating components perpendicular thereto. The linear polarizer may be either a structure using a linear polarizer alone or a structure provided with a protective film attached to at least one surface thereof on the basis of the linear polarizer. The thickness of the linear polarizer is preferably 200 μm or less, preferably 0.5 μm to 100 μm, and when the thickness exceeds 200 μm, flexibility is reduced.
The linear polarizer may be a film type polarizer manufactured by dyeing and stretching a polyvinyl alcohol (PVA) -based film. By stretching the PVA-based film aligned by stretching in a state where a dichroic dye such as iodine is adsorbed or in a state where PVA is adsorbed, the dichroic dye can be aligned to exert polarization performance. In addition, in the process of manufacturing the thin film type polarizer, it further includes: swelling, crosslinking with boric acid, washing with aqueous solution, drying, and the like. The stretching and dyeing step may be performed either by itself or in a state of being laminated with another film such as polyethylene terephthalate, and the thickness of the PVA-based film used is 10 to 100 μm and the stretching ratio is 2 to 10 times.
In addition, as another example of the polarizer, a liquid crystal coating type polarizer formed by coating a liquid crystal polarizing composition may be employed. The liquid crystal polarizing composition preferably contains a liquid crystalline compound and a dichroic dye compound, and the liquid crystalline compound preferably has a property of exhibiting a liquid crystalline state, and in particular, has a smectic equal-height difference alignment state, and can exhibit a high polarizing performance, so that the effect is very desirable. In addition, the liquid crystalline compound preferably further has a polymerizable functional group. The dichroic dye compound is a dye which exhibits dichroism by being aligned with the liquid crystal compound, and may have liquid crystallinity and may have a polymerizable functional group. One of the compounds in the liquid crystal polarizing composition has a polymerizable functional group, and the liquid crystal polarizing composition contains an initiator, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a crosslinking agent, a silane coupling agent, and the like. The liquid crystal coated polarizer may be manufactured by coating a liquid crystal polarizing composition on an alignment film to form a liquid crystal polarizer. The liquid crystal coated polarizer may be made thinner in thickness than the film type polarizer. The thickness of the liquid crystal coated polarizer is 0.5 to 10 μm, and preferably, the thickness may also be 1 to 5 μm.
The alignment film can be produced, for example, by applying an alignment film-forming composition to a substrate, and then imparting alignment properties such as rubbing (rubbing) and polarized light irradiation. The alignment film forming composition contains an alignment agent, and in addition, contains a solvent, a crosslinking agent, an initiator, a dispersant, a leveling agent, a silane coupling agent, and the like. For example: the alignment agent may be polyvinyl alcohol, polyacrylate, polyamide acid, or polyimide. If photoalignment is used, it is preferred to use an alignment agent containing cinnamyl groups. The weight average molecular weight of the polymer used as the alignment agent is about 10,000 ～ 1,000,000, and the thickness of the alignment film is 5nm to 10,000nm. In particular, when the thickness is 10 to 500nm, the alignment controlling force can be sufficiently exhibited, so that the effect is preferable. The liquid crystal polarizer can be transferred and laminated after being peeled off from the substrate, or can be directly laminated on the substrate. The substrate may also function as a protective film or a phase difference plate, or a window transparent substrate.
The protective film may be a transparent polymer film, an additive may be used as a material for the transparent substrate, and the transparent substrate may be the same as the above.
The lambda/4 phase difference plate is a film for imparting lambda/4 phase difference in a direction orthogonal to the advancing direction of the incident light (in-plane direction of the film). The lambda/4 retardation plate may be a stretched retardation plate produced by stretching a polymer film such as a cellulose film, an olefin film, or a polycarbonate film. According to need, it comprises: phase difference regulators, plasticizers, ultraviolet absorbers, infrared absorbers, pigments, dyes and other colorants, optical brighteners, dispersants, heat stabilizers, light stabilizers, antistatic agents, antioxidants, lubricants, solvents, and the like. The thickness of the stretched phase difference plate is 200 μm or less, preferably 1 μm to 100 μm, and if the thickness exceeds 200 μm, the flexibility is reduced.
In addition, as another example of the λ/4 phase difference plate, a liquid crystal coating type phase difference plate formed by coating a liquid crystal composition may be used. The liquid crystal composition comprises a liquid crystal compound having liquid crystal state properties such as nematic phase, cholesteric phase and smectic phase, one compound comprising the liquid crystal compound in the liquid crystal composition is provided with a polymerizable functional group, and the liquid crystal coating type phase difference plate further comprises an initiator, a solvent, a dispersing agent, a leveling agent, a stabilizing agent, a surfactant, a crosslinking agent, a silane coupling agent and the like. The liquid crystal coated retardation plate may be manufactured by coating a liquid crystal composition on an alignment film and hardening the composition to form a liquid crystal retardation layer, as described in the description of the liquid crystal polarizer. The thickness of the liquid crystal coating type retardation plate can be made thinner than that of the stretching type retardation plate. The liquid crystal retardation layer has a thickness of 0.5 to 10 μm, preferably 1 to 5 μm. The liquid crystal coating type retardation plate may be peeled from the substrate and then transfer-laminated, or the substrate may be directly laminated. The substrate may also function as a protective film or a phase difference plate, or a window transparent substrate.
In general, materials having a larger birefringence at a shorter wavelength and a smaller birefringence at a longer wavelength are very many. In this case, since the λ/4 phase difference cannot be achieved in all visible light ranges, the in-plane phase difference reaching the λ/4 condition around 560nm where the visibility is high is 100 to 180nm, and it is preferable to set the in-plane phase difference to be generally 130 to 150nm. In contrast to the normal case, the effect is very desirable because the recognition can be further improved by using an inverse dispersion λ/4 retardation plate using a material having an inverse-birefringent wavelength dispersion characteristic. As such a material, if it is a stretched phase difference plate, it is possible to use the one described in japanese laid-open patent No. 2007-232873 or the like; in the case of a liquid crystal coating type retardation plate, the one described in japanese laid-open patent No. 2010-30979 can be used.
As another method, a technique of obtaining a wide-band λ/4 phase difference plate by combining it with a λ/2 phase difference plate may be adopted (japanese laid-open patent publication No. 10-90521). The lambda/2 retardation plate can be produced by using the same materials and methods as the lambda/4 retardation plate, and the stretching type retardation plate and the liquid crystal coating type retardation plate can be optionally combined, but all products using the liquid crystal coating type retardation plate can be produced with a very thin thickness, and thus the effect is preferable.
In order to improve the recognition in the diagonal direction, the circular polarizer may also employ a method of laminating the positive C plate (japanese laid-open patent No. 2014-224837). The positive C plate may be a liquid crystal coated retardation plate or a stretched retardation plate. The phase difference in the thickness direction is-200 to-20 nm, preferably-140 to-40 nm.
The respective members and members (circular polarizer, linear polarizer, phase difference plate, etc.) constituting the respective members (window, display panel, touch sensor, polarizer, etc.) may be directly bonded to each other, or an adhesive layer or adhesive layer 501, 502 may be further included in each member or member in order to bond them to each other.
Although the kind of the adhesive layer or the adhesive layers 501 and 502 is not particularly limited in the present invention, the adhesive may be a widely used product such as an aqueous adhesive, an organic solvent adhesive, an inorganic solvent adhesive, a solid adhesive, an aqueous solvent volatile adhesive, a moisture curing adhesive, a thermosetting adhesive, an anaerobic curing adhesive, an active energy ray curing adhesive, a hardener mixture adhesive, a hot melt adhesive, a pressure-reducing adhesive (adhesive), a rewet adhesive, an adhesive, or the like. Among them, there are water-based solvent-volatile adhesives, active energy ray-curable adhesives, and adhesives, which are relatively commonly used. The thickness of the adhesive layer may be appropriately adjusted depending on the required adhesive force and the like, and is generally 0.01 μm to 500. Mu.m, preferably 0.1 μm to 300. Mu.m, and various adhesives may be used in the image display device, but the thicknesses of the various adhesive layers may be the same or different.
The water-based solvent-volatile adhesive may be a water-soluble polymer such as polyvinyl alcohol polymer or starch, or a water-dispersible polymer such as polyvinyl acetate emulsion or styrene-butadiene emulsion. In addition to water and the resin polymer, a crosslinking agent, a silane compound, an ionic compound, a crosslinking catalyst, an antioxidant, a dye, a pigment, an inorganic filler, an organic solvent, and the like may be formulated. If the aqueous solvent-volatile adhesive is used for bonding, the aqueous solvent-volatile adhesive is injected between the bonded layers to bond the bonded layers, and then dried, whereby the adhesive property can be imparted. When the adhesion is performed using the aqueous solvent-volatile adhesive, the thickness of the adhesive layer is 0.01 to 10 μm, preferably 0.1 to 1 μm. If multiple layers are bonded using the aqueous solvent-volatile adhesive, the thickness of each layer may be the same or different.
The active energy ray-curable adhesive may be formed by curing an active energy ray-curable composition containing a reactive substance that forms an adhesive layer after irradiation with active energy rays. The active energy ray hardening composition comprises at least 1 polymer of free radical polymerizable compounds such as hard coating compositions and cationic polymerizable compounds. The radical polymerizable compound may be used in the same manner as the hard coat composition, and various compositions such as the hard coat composition may be used. The radical polymerizable compound used in the adhesive layer is preferably an acryl-containing compound, and may contain a monofunctional compound in order to reduce the viscosity of the adhesive composition.
The cationically polymerizable compound may be used in the same manner as the hard coat composition, and various compositions such as the hard coat composition may be used. In particular, the cationically polymerizable compound used for the active energy ray-curable composition is preferably an epoxy compound. In order to reduce the viscosity of the adhesive composition, monofunctional compounds may also be used as reactive diluents.
The active energy ray composition further contains a polymerization initiator, which may be used as described above.
The active energy ray hardening composition further comprises: ion scavenger, antioxidant, chain transfer agent, tackifier, thermoplastic resin, filler, flow viscosity modifier, plasticizer, defoamer, additive, solvent, etc. If the bonding is performed by using the active energy ray-curable adhesive, the bonding may be performed by applying the active energy ray-curable composition to one or both of the layers to be bonded, and then curing the composition by irradiation of active energy rays through one or both of the layers to be bonded. When bonding is performed using the active energy ray-curable adhesive, the thickness of the adhesive layer is 0.01 to 20 μm, preferably, 0.1 to 10 μm. If multiple layers are bonded using the active energy ray-curable adhesive, the thickness of each layer may be the same or different.
The adhesive may be classified into an acrylic adhesive, a polyurethane adhesive, a rubber adhesive, a silicon adhesive, etc. depending on the kind of the resin polymer, and any one of them may be used. In addition to the resin polymer, the adhesive may be formulated with a crosslinking agent, a silane-based compound, an ionic compound, a crosslinking catalyst, an antioxidant, a tackifier, a plasticizer, a dye, a pigment, an inorganic filler, and the like. The adhesive composition can be obtained by dissolving the various components constituting the adhesive in a solvent to disperse them, and then drying the adhesive composition after coating the adhesive composition on a substrate, thereby forming an adhesive layer. The adhesive layer may be formed directly or may be transferred to another substrate. A special-shaped film may be used to cover the adhesive surface before the adhesion. If the adhesive is used, the adhesive layer has a thickness of 1 to 500 μm, preferably, a thickness of 2 to 300 μm. If multiple layers are bonded with the adhesive, the thickness of each layer may be the same or different.
Although the order of the respective components in the image display device of the present invention is not particularly limited in the present invention, as an example, it will be described with reference to fig. 1. As shown in fig. 1 (a), a structure in which a display panel 200, a lower adhesive layer 502, a touch sensor 300, a polarizer 400, an upper adhesive layer or an adhesive layer 501, and a window 100 are sequentially laminated may be employed; as shown in fig. 1 (b), a structure in which the display panel 200, the polarizer 400, the lower adhesive layer 502, the touch sensor 300, the upper adhesive layer or adhesive layer 501, and the window 100 are sequentially laminated may be employed; as shown in fig. 1 (c), a structure in which the display panel 200, the touch sensor 300, the polarizer 400, the adhesive layer or the adhesive layer 501, and the window 100 are sequentially laminated may be also employed. In this case, the specific content of each structure is as described above.
In addition, as shown in fig. 1 (a) or (c), the image display device may further sequentially configure the window 100, the polarizer 400, and the touch sensor 300 from the recognition side of the user. In this case, the sensing unit of the touch sensor 300 is disposed under the polarizer 400, so that the occurrence of the pattern blurring phenomenon can be more effectively prevented.
In the case where the touch sensor 300 includes a substrate, for example: the substrate may comprise triacetylcellulose, cycloolefins, chlorinated olefin copolymers, polynorbornene copolymers, and the like. Preferably, the front phase difference may be ±2.5nm or less, but is not limited thereto.
In addition, the touch sensor 300 may be directly transferred to the window 100 or the polarizer 400. In this case, the image display device may sequentially configure the window 100, the touch sensor 300, and the polarizer 400 from the recognition side of the user.
The display panel 200 may be joined to the various components by an adhesive layer or layers 502 in the manner shown in fig. 1 (a). In this case, for example: the adhesive layer or adhesive layer 502 has a viscoelastic property of about 0.2MPa or less at-20 to 80 c, preferably, a viscoelastic property of 0.01 to 0.15MPa. In this case, noise generated from the display panel 200 can be shielded, and interface stress can be relieved when bent, so that the bonded components can be prevented from being damaged.
The hard coating film of the present invention can satisfy the high hardness and abrasion resistance required for a hard coating layer, has excellent antistatic properties and antifouling properties, and is excellent in bending resistance, and can be suitably used for a hard coating layer for soft display treatment when used for a plastic substrate. In particular, the hard coating film according to the present invention can maintain the following excellent properties of antistatic property, stain resistance, abrasion resistance, high hardness or bending resistance.
In the following, examples will be given for the purpose of specifically explaining the present specification. However, the embodiments described in the present specification may be modified in various forms, and the scope of the present specification is not limited to the embodiments described in detail below. The purpose of the examples set forth in this specification is to more fully introduce this specification to those having ordinary skill in the art. In addition, "%" and "parts" indicating contents are weight standards unless otherwise indicated.
Manufacturing example: manufacture of hard coating compositions
Production example 1
A hard coating composition was prepared by mixing 22.75% by weight of 6-functional urethane acrylate (Shin-Nakamura Chemical, U-6 LPA), 22.75% by weight of 14-functional acrylate (manufactured by Miramer SP1106, manufactured by Miramer chemical Co., ltd.), 10% by weight of fluorine-based solvent (C6 FOH-BF, manufactured by NICCA Co.), 40% by weight of methyl ethyl ketone, 3.5% by weight of 1-hydroxycyclohexyl phenyl ketone, 0.5% by weight of ionic liquid (manufactured by DKS Co., ELEXCEL AS-804), and 0.5% by weight of fluorine-containing UV-curable functional compound (manufactured by Shin Etsu letter, KY-1203, solid 20%) with a stirrer, and then filtering with a PP-based filter.
Production example 2
A hard coating composition was prepared by mixing 22.75% by weight of 6-functional urethane acrylate (Shin-Nakamura Chemical, U-6 LPA), 22.75% by weight of 14-functional acrylate (manufactured by Miramer SP1106, manufactured by Miraber Co., ltd.), 10% by weight of fluorine-based solvent (C6 FOH-BF, manufactured by NICCA Co.), 40% by weight of methyl ethyl ketone, 3.5% by weight of 1-hydroxycyclohexyl phenyl ketone, 0.5% by weight of lithium salt (manufactured by Chunbo Co., liSSI), and 0.5% by weight of fluorine-containing UV curable functional group compound (manufactured by Shin Etsu Co., ltd., KY-1203, 20% by solid) with a stirrer, and then filtering with a PP-based filter.
Production example 3
A hard coating composition was prepared by mixing 22.75% by weight of 6-functional urethane acrylate (Shin-Nakamura Chemical, U-6 LPA), 22.75% by weight of 14-functional acrylate (manufactured by Miramer SP1106, manufactured by Miraber Co., ltd.), 10% by weight of a fluorine-based solvent (C6 FOH-BF, manufactured by NICCA Co.), 38% by weight of methyl ethyl ketone, 3.5% by weight of 1-hydroxycyclohexyl phenyl ketone, 2.5% by weight of a conductive metal oxide mixed solution (manufactured by Nissan Chemical Co., HX-204IP, 80% of a solvent other than tin oxide 20%), and 0.5% by weight of a fluorine-containing UV-curable functional group (manufactured by Shin Etsu Xinyu Co., KY-1203, 20%) with a stirrer, and then filtering with a PP-based filter.
Production example 4
A hard coating composition was prepared by mixing 22.75% by weight of 6-functional urethane acrylate (Shin-Nakamura Chemical, U-6 LPA), 22.75% by weight of 14-functional acrylate (manufactured by Miramer SP1106, manufactured by Miramer chemical Co., ltd.), 10% by weight of fluorine-based solvent (C6 FOH-BF, manufactured by NICCA Co., ltd.), 15.5% by weight of methyl ethyl ketone, 3.5% by weight of 1-hydroxycyclohexyl phenyl ketone, 25% by weight of conductive Polymer compound (Shin-Etsu Polymer Co., ltd., SAS-F16, polythiophene-resin mixture), and 0.5% by weight of fluorine-containing UV-curable functional group (Shin Etsu Xintsu Co., ltd., KY-1203, solid 20%) with a stirrer, and then filtering with a PP-based filter.
Production example 5
A hard coating composition was prepared by mixing 20.5% by weight of 6-functional urethane acrylate (Shin-Nakamura Chemical, U-6 LPA), 20.5% by weight of 14-functional acrylate (manufactured by Miramer SP1106, manufactured by Miraber Co., ltd.), 10% by weight of fluorine-based solvent (C6 FOH-BF, manufactured by NICCA Co.), 40% by weight of methyl ethyl ketone, 3.5% by weight of 1-hydroxycyclohexyl phenyl ketone, 5% by weight of ionic liquid (manufactured by DKS Co., ltd., ELEXCEL AS-804), and 0.5% by weight of fluorine-containing UV curable functional group compound (manufactured by Shin Etsu Co., ltd., KY-1203, 20% by solid) with a stirrer, and then filtering with a PP-based filter.
Production example 6
A hard coating composition was prepared by mixing 20.5% by weight of 6-functional urethane acrylate (Shin-Nakamura Chemical, U-6 LPA), 20.5% by weight of 14-functional acrylate (Miramer SP1106, manufactured by Miramer chemical Co., ltd.), 10% by weight of a fluorine-based solvent (C6 FOH-BF, manufactured by NICCA Co., ltd.), 40% by weight of methyl ethyl ketone, 3.5% by weight of 1-hydroxycyclohexyl phenyl ketone, 5% by weight of a lithium salt (manufactured by Chunbo Co., liSSI), and 0.5% by weight of a fluorine-containing UV curable functional group compound (manufactured by Shin Etsu Xinyue Co., ltd., KY-1203, 20% by solid) with a stirrer, and then filtering with a filter made of PP material.
PREPARATION EXAMPLE 7
A hard coating composition was prepared by mixing 20.5% by weight of 6-functional urethane acrylate (Shin-Nakamura Chemical, U-6 LPA), 20.5% by weight of 14-functional acrylate (manufactured by Miramer SP1106, manufactured by Miramer Chemical Co., ltd.), 10% by weight of a fluorine-based solvent (C6 FOH-BF, manufactured by NICCA Co., ltd.), 20% by weight of methyl ethyl ketone, 3.5% by weight of 1-hydroxycyclohexyl phenyl ketone, 25% by weight of a conductive metal oxide mixed solution (manufactured by Nissan Chemical Co., ltd., HX-204IP, a solvent other than tin oxide 20% 80%), and 0.5% by weight of a fluorine-containing UV-curable functional group compound (manufactured by Shin Etsu Co., ltd., KY-1203, a solid 20%) with a stirrer, and then filtering with a PP-based filter.
Production example 8
A hard coating composition was prepared by blending 22.875% by weight of 6-functional urethane acrylate (Shin-Nakamura Chemical, U-6 LPA), 22.875% by weight of 14-functional acrylate (manufactured by Miramer SP1106, manufactured by Meiyuan chemical Co., ltd.), 10% by weight of fluorine-based solvent (C6 FOH-BF, manufactured by NICCA Co., ltd.), 27.75% by weight of methyl ethyl ketone, 3.5% by weight of 1-hydroxycyclohexyl phenyl ketone, 12.5% by weight of conductive Polymer (Shin-Etsu Polymer Co., ltd., SAS-F16, polythiophene-resin mixture), and 0.5% by weight of fluorine-containing UV curable functional group (Shin Etsu Xintsu Co., ltd., KY-1203, solid content 20%) with a stirrer, and then filtering with a PP-based filter.
Production example 9
A hard coating composition was prepared by mixing 22.75% by weight of 6-functional urethane acrylate (Shin-Nakamura Chemical, U-6 LPA), 22.75% by weight of 14-functional acrylate (manufactured by Miramer SP1106, manufactured by Miramer chemical Co., ltd.), 10% by weight of a fluorine-based solvent (3M manufactured by Novec HFE-7300), 40% by weight of methyl ethyl ketone, 3.5% by weight of 1-hydroxycyclohexyl phenyl ketone, 0.5% by weight of an ionic liquid (manufactured by DKS Co., ELEXCEL AS-804), and 0.5% by weight of a fluorine-containing UV-curable functional compound (manufactured by Shin Etsu Xinyue Co., ltd., KY-1203, 20% by weight of a solid) with a stirrer, and then filtering with a PP-based filter.
Production example 10
A hard coating composition was prepared by mixing 22.75% by weight of 6-functional urethane acrylate (Shin-Nakamura Chemical, U-6 LPA), 22.75% by weight of 14-functional acrylate (manufactured by Miramer SP1106, manufactured by Mesource specialty chemical Co., ltd.), 10% by weight of fluorine-based solvent (3M manufactured by Novec HFE-7300), 40% by weight of methyl ethyl ketone, 3.5% by weight of 1-hydroxycyclohexyl phenyl ketone, 0.5% by weight of lithium salt (manufactured by chunbo Co., liSSI), and 0.5% by weight of fluorine-containing UV curable functional group compound (manufactured by Shin Etsu Co., ltd., KY-1203, solid 20%) with a stirrer, and then filtering with a PP-based filter.
Production example 11
A hard coating composition was prepared by mixing 22.75% by weight of 6-functional urethane acrylate (Shin-Nakamura Chemical, U-6 LPA), 22.75% by weight of 14-functional acrylate (manufactured by Miramer SP1106, manufactured by Miramer Chemical Co., ltd.), 10% by weight of a fluorine-based solvent (3M manufactured by Novec HFE-7300), 38% by weight of methyl ethyl ketone, 3.5% by weight of 1-hydroxycyclohexyl phenyl ketone, 2.5% by weight of a conductive metal oxide mixed solution (manufactured by Nissan Chemical Co., HX-204IP, 80% of a solvent other than tin oxide) and 0.5% by weight of a fluorine-containing UV curable functional group (manufactured by Shin Etsu Xinyue Co., KY-1203, 20% of a solid) with a stirrer, and then filtering with a PP-based filter.
Production example 12
A hard coating composition was prepared by blending 22.75% by weight of 6-functional urethane acrylate (Shin-Nakamura Chemical, U-6 LPA), 22.75% by weight of 14-functional acrylate (manufactured by Miramer SP1106, manufactured by Miramer chemical Co., ltd.), 10% by weight of a fluorine-based solvent (3M manufactured by Novec HFE-7300), 15.5% by weight of methyl ethyl ketone, 3.5% by weight of 1-hydroxycyclohexyl phenyl ketone, 25% by weight of a conductive Polymer compound (Shin-Etsu Polymer Co., ltd., SAS-F16, a polythiophene-resin mixture), and 0.5% by weight of a fluorine-containing UV curable functional group (Shin Etsu Xinyue Co., ltd., KY-1203, solid content 20%) with a stirrer, and then filtering with a PP-based filter.
PREPARATION EXAMPLE 13
A hard coating composition was prepared by mixing 15.5% by weight of 6-functional urethane acrylate (Shin-Nakamura Chemical, U-6 LPA), 15.5% by weight of 14-functional acrylate (Miramer SP1106, manufactured by Miramer chemical Co., ltd.), 10% by weight of a fluorine-based solvent (3M, manufactured by Novec HFE-7300), 40% by weight of methyl ethyl ketone, 3.5% by weight of 1-hydroxycyclohexyl phenyl ketone, 15% by weight of a lithium salt (manufactured by chunbo, liSSI), and 0.5% by weight of a fluorine-containing UV curable functional group compound (manufactured by Shin Etsu, KY-1203, 20% by solid) with a stirrer, and then filtering with a PP-based filter.
PREPARATION EXAMPLE 14
A hard coating composition was prepared by blending 23 wt% of 6-functional urethane acrylate (Shin-Nakamura Chemical, U-6 LPA), 23 wt% of 14-functional acrylate (Miramer SP1106, manufactured by Miraber Co., ltd.), 10 wt% of a fluorine-based solvent (C6 FOH-BF, manufactured by NICCA Co., ltd.), 40 wt% of methyl ethyl ketone, 3.5 wt% of 1-hydroxycyclohexyl phenyl ketone, and 0.5 wt% of a fluorine-containing UV-curable functional compound (Shin Etsu Xinyue Co., ltd., KY-1203, solid content 20%) with a stirrer, and then filtering with a PP-based filter.
Production example 15
A hard coating composition was prepared BY blending 22.75% BY weight of 6-functional urethane acrylate (Shin-Nakamura Chemical, U-6 LPA), 22.75% BY weight of 14-functional acrylate (Miramer SP1106, manufactured BY Mei Yuan chemical Co., ltd.), 10% BY weight of fluorine-based solvent (C6 FOH-BF, manufactured BY NICCA Co.), 40% BY weight of methyl ethyl ketone, 3.5% BY weight of 1-hydroxycyclohexyl phenyl ketone, 0.5% BY weight of ionic liquid (manufactured BY DKS Co., ELEXCEL AS-804), and 0.5% BY weight of silicon-based leveling agent (manufactured BY BYK Co., ltd., BY-307) with a stirrer, and then filtering with a filter made of PP material.
Examples and comparative examples
Example 1
The hard coating composition produced according to production example 1 was hardened on a polyester film (PET, 50 μm) and then coated to a thickness of 5 μm, followed by drying the solvent at 80 ℃ for 2 minutes. Then, the UV integrated light quantity was 600mJ/cm under nitrogen atmosphere 2 A hard coat film was produced.
Example 2
The hard coating composition liquid produced according to production example 2 was hardened on a polyester film (PET, 50 μm) and then coated to a thickness of 5 μm, followed by drying the solvent at 80 ℃ for 2 minutes. Then, the UV integrated light quantity was 600mJ/cm under nitrogen atmosphere 2 A hard coat film was produced.
Example 3
The hard coating composition liquid produced according to production example 3 was hardened on a polyester film (PET, 50 μm) and then coated to a thickness of 5 μm, followed by drying the solvent at 80 ℃ for 2 minutes. Then, the UV integrated light quantity was 600mJ/cm under nitrogen atmosphere 2 A hard coat film was produced.
Example 4
The hard coating composition liquid produced according to production example 4 was hardened on a polyester film (PET, 50 μm) and then coated to a thickness of 5 μm, followed by drying the solvent at 80 ℃ for 2 minutes. Then, the UV integrated light quantity was 600mJ/cm under nitrogen atmosphere 2 A hard coat film was produced.
Example 5
The hard coating composition liquid produced according to production example 5 was hardened on a polyester film (PET, 50 μm) and then coated to a thickness of 5 μm, followed by drying the solvent at 80 ℃ for 2 minutes. Then, the UV integrated light quantity was 600mJ/cm under nitrogen atmosphere 2 A hard coat film was produced.
Example 6
The hard coating composition liquid produced according to production example 6 was hardened on a polyester film (PET, 50 μm) and then coated to a thickness of 5 μm, followed by drying the solvent at 80 ℃ for 2 minutes. Then, the UV integrated light quantity was 600mJ/cm under nitrogen atmosphere 2 A hard coat film was produced.
Example 7
The hard coating composition liquid produced according to production example 7 was hardened on a polyester film (PET, 50 μm) and then coated to a thickness of 5 μm, followed by drying the solvent at 80 ℃ for 2 minutes. Then, the UV integrated light quantity was 600mJ/cm under nitrogen atmosphere 2 A hard coat film was produced.
Example 8
The hard coating composition liquid produced according to production example 8 was hardened on a polyester film (PET, 50 μm) and then coated to a thickness of 5 μm, followed by drying the solvent at 80 ℃ for 2 minutes. Then, the UV integrated light quantity was 600mJ/cm under nitrogen atmosphere 2 A hard coat film was produced.
Example 9
The hard coating composition liquid produced according to production example 9 was hardened on a polyester film (PET, 50 μm) and then coated to a thickness of 5 μm, followed by drying the solvent at 80 ℃ for 2 minutes. Then, the UV integrated light quantity was 600mJ/cm under nitrogen atmosphere 2 A hard coat film was produced.
Example 10
The hard coating composition liquid produced according to production example 10 was hardened on a polyester film (PET, 50 μm) and then coated to a thickness of 5 μm, followed by drying the solvent at 80 ℃ for 2 minutes. Then, the UV integrated light quantity was 600mJ/cm under nitrogen atmosphere 2 A hard coat film was produced.
Example 11
The hard coating composition liquid produced according to production example 11 was hardened on a polyester film (PET, 50 μm) and then coated to a thickness of 5 μm, followed by drying the solvent at 80 ℃ for 2 minutes. Then, the UV integrated light quantity was 600mJ/cm under nitrogen atmosphere 2 A hard coat film was produced.
Example 12
The hard coating composition liquid produced according to production example 12 was hardened on a polyester film (PET, 50 μm) and then coated to a thickness of 5 μm, followed by drying the solvent at 80 ℃ for 2 minutes. Then, the UV integrated light quantity was 600mJ/cm under nitrogen atmosphere 2 A hard coat film was produced.
Example 13
Hard coating composition produced according to production example 13The solution was cured on a polyester film (PET, 50 μm) and then coated to a thickness of 5 μm, followed by drying the solvent at 80℃for 2 minutes. Then, the UV integrated light quantity was 600mJ/cm under nitrogen atmosphere 2 A hard coat film was produced.
Comparative example 1
The hard coating liquid produced according to production example 14 was hardened on a polyester film (PET, 50 μm) and then coated to a thickness of 5 μm, followed by drying the solvent at 80℃for 2 minutes. Then, the UV integrated light quantity was 600mJ/cm under nitrogen atmosphere 2 A hard coat film was produced.
Comparative example 2
The hard coating liquid produced according to production example 15 was hardened on a polyester film (PET, 50 μm) and then coated to a thickness of 5 μm, followed by drying the solvent at 80℃for 2 minutes. Then, the UV integrated light quantity was 600mJ/cm under nitrogen atmosphere 2 A hard coat film was produced.
Experimental example
(1) Stain resistance
The hard coat layer was placed on the upper portion, and the contact angle of water was measured by a contact angle measuring instrument DSA100 manufactured by KRUSS corporation. The amount of the droplets was set to 3. Mu.l at normal temperature, and the results are shown in Table 1. At this time, the larger the water contact angle is, the lower the surface energy of the hard coating surface is, and therefore, it is known that the larger the water contact angle is, the more excellent the antifouling property is.
(2) Wear resistance
The hard coating layer was placed on the upper part, and the wear resistance was measured by a wear resistance measuring device manufactured by the company of Dasheng precision equipment. Specifically, the surface of the hard coating was rubbed 3000 times with a weight of 1kg of a weight using a rub-off wiper for abrasion resistance test, and then the water contact angle was measured. The amount of the droplets was 3. Mu.l at room temperature, and the results are shown in Table 1.
(3) Hardness of pencil
After fixing the base film to the glass so that the hard coat surface was positioned on the upper portion, pencil hardness was measured under a load of 1 kg. The pencil hardness was measured 5 times at a length of 1cm using pencils of the same hardness, and pencil hardness not scraped 4 times or more was used as pencil hardness of the final film, and the results are shown in table 1.
(4) Scratch resistance
After the base film was bonded to glass with a transparent adhesive so that the hard coat surface was positioned on the upper portion, the base film was bonded to glass with a steel wool (# 0000) at 500g/cm 2 The scratch resistance is determined by rubbing back and forth 10 times under the load condition. The evaluation criteria were as follows:
the measurement section was allowed to pass through the three-wavelength tube and reflected, and no scratch or less than 10 scratches were recognized when observed.
X. the measurement part was allowed to pass through a three-wavelength tube and reflected, and the number of scratches recognized in observation was more than 10.
(5) Adhesion properties
After the base film was bonded to the glass with a transparent adhesive so that the hard coat surface was positioned on the upper portion, 100 square scratches were formed on the hard coat surface in the lateral and longitudinal directions at 1mm intervals by a doctor blade, and 3 adhesion (peeling) tests were performed with an adhesive tape (CT-24, manufactured by milpa company, japan) and 3 out of 100 square scratches were selected for testing, and the average value was recorded.
Adhesion = n/100
n is the number of non-stripped squares in the total square scratch.
100 is the number of all squares.
(6) Bending resistance
The hard coat layer was folded inward, and the film was subjected to repeated folding and unfolding tests for 20 ten thousand times with a radius of curvature of 1mm, whereby the film was evaluated for breaking or not according to the following evaluation criteria, and the results are shown in table 1.
< evaluation criteria >
O: no breakage occurs
X: breaking occurs
(7) Surface impedance
The surface resistivity of the hard coat layer was measured by applying a voltage of 500V using a mitsubishi surface resistance measuring instrument (MCP-HT 450, mitsubishi chemical analysis technique), and the results are shown in table 1. (Unit: Ω/≡)
TABLE 1
Figure BDA0002703934900000301
/>
Figure BDA0002703934900000311
As can be seen from the table 1, the hard coating film according to the present invention has excellent antistatic effect while also being very excellent in abrasion resistance.
Symbol description
100:200:display panel
300:400:polarizer for touch sensor
501. 502 adhesive layer or adhesive layer

Claims (6)

1. A hard coat film comprising:
a substrate; and
a hard coat layer provided on at least one surface of the base material,
the surface resistivity of the hard coating is 10 8 ～10 12 Omega/≡, the water contact angle is at least 100 DEG, and the water contact angle of the hard coating is at least 100 DEG after rubbing for 3000 times under a load of 1kg with a wiper,
wherein the hard coating comprises a hardened substance of a hard coating composition, and the hard coating composition comprises a fluorine-containing UV hardening functional group compound, a fluorine-containing solvent and an antistatic agent;
wherein the fluorine-containing UV curable functional group-containing compound is contained in an amount of 0.01 to 30% by weight relative to 100% by weight of the total solids in the hard coating composition,
the fluorine-based solvent is contained in an amount of 10 to 50% by weight relative to 100% by weight of the whole hard coating composition; and is also provided with
Wherein the fluorine-based solvent includes at least one selected from chemical formulas 1 to 8:
[ chemical formula 1]
Figure FDA0004172070240000011
[ chemical formula 2]
Figure FDA0004172070240000012
[ chemical formula 3]
Figure FDA0004172070240000013
[ chemical formula 4]
Figure FDA0004172070240000021
[ chemical formula 5]
Figure FDA0004172070240000022
[ chemical formula 6]
Figure FDA0004172070240000023
[ chemical formula 7]
Figure FDA0004172070240000024
[ chemical formula 8]
Figure FDA0004172070240000031
2. The hard coat film according to claim 1, wherein the surface resistivity of the hard coat layer is 10 9 ～10 12 Ω/□。
3. The hard coat film according to claim 1, wherein the fluorine-containing UV curable functional group-containing compound comprises: at least one selected from the group consisting of perfluoroalkyl group-containing (meth) acrylates, perfluoropolyether group-containing (meth) acrylates, perfluorocyclic aliphatic group-containing (meth) acrylates, and perfluoroaromatic group-containing (meth) acrylates.
4. The hard coat film according to claim 1, wherein the hard coat composition further comprises at least one selected from the group consisting of a light-transmitting resin, a photoinitiator, an additional solvent, and an additive.
5. A window comprising the hard coat film according to any one of claims 1 to 4.
6. An image display device comprising the window according to claim 5 and a display panel,
the touch sensor and the polaroid are arranged between the window and the display panel.
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